Process of producing combined shades of azodyestuffs and vat dyestuffs on the vegetable fiber and in materials dyed or printed according to such process



Patented Aug. 30, 1927 UNITED STATES PATENT OFFICE.

MANY, ASSIGNORS TO I. G. FARBENINDUSTRIE AKTIENGESELLSCHAFT, OF FRANK-ron'r, GERMANY.

PROCESS OF PRODUCING COMBINED SHADES OF AZODYESTUFFS. AND VAT DYESTUFFSI ON THE VEGETABLE FIBER AND IN MATERIALS DYED OR PRINTED ACCORDING TOSUCH PROCESS.

No Drawing. Original application filed December 15, 1924, Serial No.756,049, and in Germany February 1, 1924. Divided and this applicationfiled June 24, 1925. Serial No. 39,377.

Our invention relates to a process of producing combined shadesofazodyestufis and vat dyestuffs on the vegetable fiber consisting inimpregnating the fiber with an alkaline solution of an azo-component,develop- J ing with a diazo-solution, an ester-saltof the leuco-compoundof a vat dyestut'i being added to'one of the said solutions and intreating the fiber with oxidizing agents in I an acid'me dium. Ourinvention also relates to the product of such process. Ester-salts ofthe leuco-compounds of vat dyestuffs, which are prepared by transformingleuco-compounds of vat dyestuffs into acid esters of a polybasic acid,are described in the U. S. A. Letters Patent No. 1,448,251 of MarcelBader and Charles Sunder, dated Mar. 13, 1923. Our present applicationis a division of our application Serial No. 756,049 tiled in the UnitedStates Patent Office on December 15, 1924. Our invention may be used fordyeing as well as for printing, yielding excellently fast combinedcolors of different shades, which are not known hitherto, and making itpossible to supply the consumer in the most concentrated form withproducts immediately ready for use by simple operations.

In order to illustrate the new process more fully the following examplesare given. EXAMPLE 1.

The unprepared goods .are printed with the following printing color:

l0 gr. of 4-oxy naphthalene-1- are mixed withcc. of caustic sodasolution of .34 B., 30 gr. of Turkey redfl oil and 200 gr. of Water,poured in 500 gr. of neutral tragacanth thickening and henyl-ketone 4010 gr. of the product, prepared from indigo according to the U. S. A.Letters Patent No. 1,448,251, dissolved in 220 gr. of water, are addedand the whole is made up to I Then the goods'are printed with a secondprint ng-color:

165 gr. of water are added and the whole is made up to The goods aredried and passed in a lukewarm to'boiling bath containing for example 25to 30 gr. of sodium bisulfate, 30 to 40 cc. of a solution of nitrate ofiron of 20 B. in the liter, rinsed, soaped and dried.

A chocolate-brown is'obtained.

EXAMPLE 2. l A

The unprepared goods are printed'with:

10 gr. of benzoyl 2. 3 aminonaphthol are mixed with I I I 30 cc. ofcaustic soda solution of 34 B.,- 30 gr. of Turkey'red oil and A I 200gr. of water, poured in 500 gr. of neutral tragacanth thickening and 10gr. of the product, prepared from-indigo according to the U. S. A.Letters Patent No. 1,448,251, dissolved in i 220 gr. of water, are addedand the whole is made up to.

"100p gr.

. 1 The with:

. '10 gr..of 4-nitro-L2-anisidin are dissolved with 1 v I 15 gr. ofhydrochloric acid of 22 B. and 100 gr. of boiling water, I I 160 gr. ofice and after-cooling down 25 cc. of sodium nitrite 1 4 are added; the Idiazotation being complete, the mass is poured in 500 gr. of neutraltragacanth thickening,

25 rgr. of sodium acetate and 165 gr. of water are added and the whole Imade up to The goodsare dried andpassed in a developing-bath of asimilar composition as above described, or containing other likewiseacting oxidizing agents, rinsed, soaped and dried.

A dark reddish brown is obtained.

' EXAMPLE 3.

.The goods are prepared with a solution of of2.5-dithlorophenyl-3-1nethyl-5 pyrazolon in 15 cc. of caustic sodasolution of 34 Be. by addition of 10 gr. of Turkey red oil and 8 gr. ofthe product, prepared from indigo according to the U. S. A. Let-' tersPatent No. 1,448,251, in the liter. I

I The goods are dried and printed; with:

The goods are dried and ssedin the mentioned developing-bath, rinsed,swiped,

rinsed and dried.

- A green upon a blue'ground is obtained.

The goods are prepared with a solution of 10 gr. of aceto-ectyl-anilinin 15 gr. of caustic adding 10 gr;

soda ,solution of 34 B. by of Turkey red oil in the liter.

goods are dried and printed once more gr. of sodium nitriteof a standardof The goods are dried and printed with: '10 gr. of 5-nitro-1.2-toluidin are mixed with. I f 25 gr. of hot water and f 5 gr.of-jsodium nitrite, poured in 350 gr. of water and Y 530 cc. ofhydrochloric acid of 20 B.;

"the diazotation being complete the 4 mass isstirred in 450 gr. ofneutral tragacanth thickening, gr. of sodium acetate 1 :1 and 1O gr.- ofthe product, prepared from indigo according to the U. S. A. LettersPatent No. 1,448,251, dissolved m I I 50 gr. of water, are added and ismade'up to the whole 1000. gr. I

The goods arev dried and passed ,in the mentioned developing-bath,mused, soaped, rinsed and dried. I p

r A yellowish green is obtained.

By using 10 gr. of the product, prepared from dibromindigo accordingtothe U. S. A.

Letters Patent No. 1,448,251, instead of thev mentionedindigoderivative, a little more yellowish shades of a greater clearnessare obtained. I

' EXAMPLE 5.

The. goods. are impregnated with a so'lu- Ltion of 10 gr. ofaceto-a-cetyl-para anisidin in '15 cc. of caustic soda solution of 34.B. by adding 10 gr. of Turkey red oil in the liter.

' The goods are dried and printed with:

10 gr. of the product, prepared from indigo according to the U. S. A.Letters Patent No. 1,448,251, dissolved in I I 490 gr. of water, pouredin 500 gr. of neutral made up to 1000; 1-. I I I he goods" are dried andPrinted once more with: I 7 1 '13 "gnbil ortho-chloroanilin aredissolved wit 1 30 gr. of hot'water and i 30 cc. of hydrochloric acid 20B6. 140 gr. of cold water, a I 150' gr. of icev and after cooling down'7, 5 gr. of sodium nitrite and 30 gr; of water are added;thediaaotation' 1 being'compleoe the mass is poured in I 450 gr. of neutraltragacanth thickening,

50 cc. of sodium acetate 1 :1 are added and the whole is made .up totragacan th thickening,

The goods are dried, passed in tioned developing-bath, rinsed, rinsedand dried.

Blue, green and yellow printing-effects on a white-ground are obtained.

soaped,

ExAMrLE 6.

' The goods are then printed with the following printing-color: I

10 gr. of meta-nitro-ortho-anisidin (OCH NH NO =1 :2 z 4) are dis solvedwith 1 gr. of hydrochloric acid of 22 B. and

gr. of boiling water and gr. of ice are added. After cooling down whilestirring cc. of sodium nitrate 1:4 are added. The .diazotation beingcomplete, the mass is poured in gr. of neutral tragacanth thickening,

neutralized with 25 gr. of sodium acetate and 20 gr. of the product,prepared from indigio, according to the U. S. A. Letters Patent No.1,448,251, dissolved 145 gr. of water, are added and the whole is madeup to The goods are dried, steamed for a short while and passed into thementioned developing-bath, rinsed, soaped and dried.

A dark violet of an excellent fastness is obtained.

EXAMPLE 7 v The cotton goods are prepared with the following solutionand .dried.

Padding-solution 1. a 10 gr. of 'diacetoacetyl-ortho-tolidin, 12

cc. of caustic soda solution of 34 'B., 10

ters Patent No. 1,448,251, dissolved I in gr. of water, are added andthe whole is made up to the men- The goods are dried, steamed for ashort wlliile and ve oping-bat dried.-

A light green shade of aniexcellent fastness is obtained.

EXAMPLE 8.

The unprepared ,goods are printed with the following printing-color anddried:

Printing-color 1.

, rinsed, soaped, rinsed and passed into the mentioned de-- 110 gr. ofmeta-nitroanilid of 2.3-oxyna-ph- I thoic acid, 12 cc. of caustic sodasolution of 34 B., 10 gr. of Turkey red oil are dissolved in 200 gr. ofboiling water and poured in 500 gr. of neutral tragacanth thickening.

After cooling down 10 gr. of the product, prepared from indigo accordingto the U. S. A. Letters Patent No. 1,448,251, dissolved m 2 58 gruofwater, are added and the whole r is made up to The goods are printedonce more with a second printing-color or padded with a correspondingsolution.

Printing- 0201- 2. v i 50 gr. of the diazo-salt of 2.5-dichloroanilinare dissolved in 450 gr. of water and poured in 500 gr. of a neutraltragacanth thickening and the whole is made up to a The goods are driedand passed into a lukewarm to .boiling bath, containing 3 gr. of ironchloride, 1 gr. of bichromate, 25 gr. of sodium bisulfate. 1 liter,rinsed, soaped and dried. v

A reddish brown of an excellent fastness is obtained.

' EXAMPLE-9.

"The unprepared goods are printed with the following printing-color:

Pfinting-oolo'r 1. 10 gr. Of diacetoacetyl-ortho-tolidin, 12 cc. ofcaustic soda solution of 34 B., 10 gr. of Turkey red oil are dissolvedin 200 gr. of boiling water and poured in 500 gr. of neutral tragacanththickening.

After cooling down *10gr. of the product, prepared from indigo accordingto the U. S. A. Letters Patent No. 1,448,251, dissolved in v 258 gr. ofwater, are added and'the whole is made .to

iooo r, I i

' The goods are printed with a second and the components thereofnumerous furprinting-color or padded with a corresponding solution. e v

ramin -5020a 2. gr. of metra-nitro-ortho anisidin zNH zNO l :2 aredissolved with gr. of hydrochloric acidof 22 B. and 100 gr. of boilingwater,

165 gr. of Goldwater, 160 gr. of ice are added, -after cooling down I 25cc. of sodium nitrite 114;, poured in 500 gr. odf neutral tragacanththickening,

. an v 2,5 gnof sodium acetate are added and the whole is-made up to I1000 gr. I 1

The goodsare dried and passed into the bath mentioned in example 8,rinsed, soaped and dried. j

A. green of an excellent fastness is obtained. I 3 By varying theproportions'of mixtures ther shades can beobtained.

Inthe same manner, as the ester-salt of the leuco derivative of indigo,the corresponding derivatives of the halogenated indigos, thioindigo andother vat dyestuffs can be used. 'As suitable oxidizing agents we maymention: hydrogenperoxide, perborates, persulfates or chlorates,chromates. and soon.

An appropriate oxidizing agent may also be added to t-heprinting-colors. Then as developing-baths only accordingly diluted acidsor solutions of salts, acting as acids,

. may be used.

Now What weclaim and desire to secure by Letters Patent isthe following:

1. A process of producing combined shades of azodyestufis and vatdyestuffs on 'thewegetablefiber consisting in impregnating the fiberWith an alkaline solution of an azo-component, developing with adiazo-solution, an .ester-saltof the leucocompound oi": a vat dyestufii'being added to one i of said solutions and in treating the fiber withoxidizing agents in an acid medium.

2. Materials dyed with an azodyestufl' and a vat dyestuff according toclaim 1, said .Idyestufis being developed on the fiber of the material.

' i GUSTAV PETZOLD.

-' HEINRICH RITTNER.

